全文获取类型
收费全文 | 442篇 |
免费 | 18篇 |
国内免费 | 2篇 |
专业分类
化学 | 390篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 9篇 |
物理学 | 58篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 17篇 |
2021年 | 23篇 |
2020年 | 16篇 |
2019年 | 16篇 |
2018年 | 8篇 |
2017年 | 12篇 |
2016年 | 16篇 |
2015年 | 8篇 |
2014年 | 15篇 |
2013年 | 24篇 |
2012年 | 38篇 |
2011年 | 38篇 |
2010年 | 25篇 |
2009年 | 23篇 |
2008年 | 34篇 |
2007年 | 29篇 |
2006年 | 29篇 |
2005年 | 21篇 |
2004年 | 22篇 |
2003年 | 5篇 |
2002年 | 7篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有462条查询结果,搜索用时 15 毫秒
71.
MF Miller IA Franchi AS Sexton CT Pillinger 《Rapid communications in mass spectrometry : RCM》1999,13(13):1211-1217
The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd. 相似文献
72.
Stephen R. Wassall Saame Raza Shaikh Michael R. Brzustowicz Vadim Cherezov Rafat A. Siddiqui Martin Caffrey William Stillwell 《Macromolecular Symposia》2005,219(1):73-84
Unequal affinity between lipids has been hypothesized to be a mechanism for the formation of microdomains/rafts in membranes. Our studies focus upon the interaction of cholesterol with polyunsaturated fatty acid (PUFA)-containing phospholipids. They support the proposal that steric incompatibility of the rigid steroid moiety for highly disordered PUFA chains, in particular docosahexaenoic acid (DHA), provides a sensitive trigger for lateral segregation of lipids into PUFA-rich/sterol-poor and PUFA-poor/sterol-rich regions. Solid state 2H NMR and x-ray diffraction (XRD) demonstrate that the solubility of cholesterol is reduced in 1-palmitoyl-2-docosahexaenoyl-phosphatidylethanolamine (16-0:22:6PE) bilayers. In mixed membranes of phosphatidylethanolamine (PE) with the lipid raft forming molecules egg sphingomyelin (SM) and cholesterol, diminished affinity of the sterol for 16:0-22:6PE relative to 1-palmitoyl-2-oleoylphosphatidylethanolamine (16:0-18:1PE) is identified by 2H NMR order parameters and detergent extraction. Phase separation of the PUFA-containing phospholipid from SM/cholesterol rafts is the implication, which may be associated with the myriad of health benefits of dietary DHA. 相似文献
73.
74.
Victoria L. Luck David P. Richards Ashif Y. Shaikh Henrik Franzyk Ian R. Mellor 《Molecules (Basel, Switzerland)》2021,26(22)
Alterations in the polyamine and amino acid (tyrosine) moieties of philanthotoxin-343 (PhTX-343) were investigated for their effects on the antagonism of nicotinic acetylcholine receptors (nAChRs) isolated from the locust (Schistocerca gregaria) mushroom body. Through whole-cell patch-clamp recordings, the philanthotoxin analogues in this study were shown to cause inhibition of the inward current when co-applied with acetylcholine (ACh). PhTX-343 (IC50 = 0.80 μM at −75 mV) antagonised locust nAChRs in a use-dependent manner, suggesting that it acts as an open-channel blocker. The analogue in which both the secondary amine functionalities were replaced with methylene groups (i.e., PhTX-12) was ~6-fold more potent (IC50 (half-maximal inhibitory concentration) = 0.13 μM at −75 mV) than PhTX-343. The analogue containing cyclohexylalanine as a substitute for the tyrosine moiety of PhTX-343 (i.e., Cha-PhTX-343) was also more potent (IC50 = 0.44 μM at −75 mV). A combination of both alterations to PhTX-343 generated the most potent analogue, i.e., Cha-PhTX-12 (IC50 = 1.71 nM at −75 mV). Modulation by PhTX-343 and Cha-PhTX-343 fell into two distinct groups, indicating the presence of two pharmacologically distinct nAChR groups in the locust mushroom body. In the first group, all concentrations of PhTX-343 and Cha-PhTX-343 inhibited responses to ACh. In the second group, application of PhTX-343 or Cha-PhTX-343 at concentrations ≤100 nM caused potentiation, while concentrations ≥ 1 μM inhibited responses to ACh. Cha-PhTX-12 may have potential to be developed into insecticidal compounds with a novel mode of action. 相似文献
75.
Rashmi C. Kulkarni S. Samundeeswari Farzanabi Shaikh Nirmala S. Naik Jyoti M. Madar Lokesh A. Shastri Vinay A. Sunagar 《Journal of fluorescence》2017,27(5):1613-1619
A variety of new coumarin derivatives containing C-4 bridged 2,6-dicyanoanilines (4a-4d) were synthesized via multicomponent one pot approach. These novel sensors were characterized by spectral analysis and a series of pH sensing fluorescence studies were performed, the results indicating that the sensors are highly selective and more effective at various pH. The fluorescence colour changes at different pH could be directly detected by naked eyes. 相似文献
76.
Shaukat Mahmood Nek M. Shaikh M.A. Kalyar M. Rafiq N.K. Piracha M.A. Baig 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(17):1840-1850
In the present work emission and absorption spectroscopy have been used to determine the plasma parameters of neon in a hollow cathode discharge lamp. The excitation temperature is determined using the intensity ratio method and Boltzmann's plot method whereas the electron density is determined from the Stark broadening of the spectral lines. The behavior of the optogalvanic signal as a function of laser energy has been studied for three transitions from the 2p53s [1/2]2 metastable state following ΔJ=ΔK=0, ±1 dipole selection rules. The saturation technique has been used to measure the photoionization cross section from three intermediate states 2p53p′ [1/2]1, 2p53p′ [3/2]2 and 2p53p [5/2]3 up to the 2p5 2P1/2 ionization threshold. 相似文献
77.
NaIO4-mediated selective oxidation of alkylarenes and benzylic bromides/alcohols to carbonyl derivatives using water as solvent 总被引:1,自引:0,他引:1
A new transition-metal-free, sodium metaperiodate (NaIO4)-mediated direct oxidation of methylarenes and benzylic bromides to the corresponding aromatic carboxylic acids is described. Under the same reaction conditions, benzylic alcohols are selectively oxidized to afford the corresponding aldehydes in good yields without undergoing overoxidation. Unprecedentedly, oxidation of benzyl bromide, toluene, or benzyl alcohol with NaIO4 underwent nuclear bromination followed by oxidation to give 4-bromobenzoic acid in 60-79% yields. 相似文献
78.
A one-pot, two-step, three-component method for the conversion of commercially available aldehydes to phosphonylpyrazoles has been developed, demonstrating, for the first time, the dual reactivity of the Bestmann-Ohira reagent (BOR) in a single-pot transformation. This method, extended to the synthesis of sulfonylpyrazoles by employing BOR in the first step and a diazomethyl sulfone in the second step, is complementary, with regard to regioselectivity, to the previous methods for the synthesis of such functionalized pyrazoles. 相似文献
79.
80.
Dhayal V Chaudhary A Choudhary BL Nagar M Bohra R Mobin SM Mathur P 《Dalton transactions (Cambridge, England : 2003)》2012,41(31):9439-9450
[Zr(OPr(i))(4)·Pr(i)OH] reacts with [HOSi(O(t)Bu)(3)] in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy zirconosiloxane precursors of the types [Zr(OPr(i))(3){OSi(O(t)Bu)(3)}] (A) and [Zr(OPr(i))(2){OSi(O(t)Bu)(3)}(2)] (B), respectively. Further reactions of A or B with glycols in 1:1 molar ratio afforded six chemically modified precursors of the types [Zr(OPr(i))(OGO){OSi(O(t)Bu)(3)}] (1A-3A) and [Zr(OGO){OSi(O(t)Bu)(3)}(2)] (1B-3B), respectively [where G = (-CH(2)-)(2) (1A, 1B); (-CH(2)-)(3) (2A, 2B) and (-CH(2)CH(2)CH(CH(3)-)} (3A, 3B)]. The precursors A and B are viscous liquids, which solidify on ageing whereas the other products are all solids, soluble in common organic solvents. These were characterized by elemental analyses, molecular weight measurements, FAB mass, FTIR, (1)H, (13)C and (29)Si-NMR studies. Cryoscopic molecular weight measurements of all the products, as well as the FAB mass studies of 3A and 3B, indicate their monomeric nature. However, FAB mass spectrum of the solidified B suggests that it exists in dimeric form. Single crystal structure analysis of [Zr{OSi(O(t)Bu)(3)}(4)(H(2)O)(2)]·2H(2)O (3b) (R(fac) = 11.9%) as well as that of corresponding better quality crystals of [Ti(O(t)Bu){OSi(O(t)Bu)(3)}(3)] (4) (R(fac) = 5.97%) indicate the presence of a M-O-Si bond. TG analyses of 3A, B, and 3B indicate the formation of zirconia-silica materials of the type ZrO(2)·SiO(2) from 3A and ZrO(2)·2SiO(2) from B or 3B at low decomposition temperatures (≤200 °C). The desired homogenous nano-sized zirconia-silica materials [ZrO(2)·nSiO(2)] have been obtained easily from the precursors A and B as well as from the glycol modified precursors 3A and 3B by hydrolytic sol-gel process in organic media without using any acid or base catalyst, and these were characterized by powder XRD patterns, SEM images, EDX analyses and IR spectroscopy. 相似文献